SU787374A1 - Method of detecting antimony compounds in ores and their processing products - Google Patents

Description

one

The invention relates to methods for determining the content of individual antimony compounds in ore materials and can be used in phase analysis of antimony ores, including Jamsonite type, rocks containing ores and enrichment products, for geochemical studies and in determining technological parameters.

A known method for the separate determination of various mineral forms of cypbNM is that a portion of the starting material is treated at the boiling point with a solution of tartaric acid. At the same time, all oxidized antimony minerals are transferred to the solution, and the rest is antimony sulfide cq.

There is also known a method for the phase analysis of antimony compounds in slags and other pyrometallurgical products, which consists in the sequential treatment of a weighed Hn with a solution of hydrochloric acid in an atmosphere of COij, Hn. hydrochloric acid solution containing 5% hydrogen peroxide and 3% solution at boiling, with the definition in filtrates of antimony trioxide, metallic antimony, sulfide antimony, and

in the balance of the antimony of the highest oxides 2.

The closest to the proposed technical essence is the method for determining the content of antimony compounds in mineral raw materials, which means that the analysis of antimony ores and their enrichment products are carried out using three batches. One sample is drawn for 16-18 hours with 50 ml of 1.5N. tartaric acid solution and valentineite antimony in the filtrate, the second sample is boiled with 50 ml of 10% NapS solution for 2 h, the amount of antimony of valentineite, antimonite and cermantite is determined in the filtrate, and the third sample of bentromaseite in the residue t t 10 -min with 2n. caustic soda solution and determined in the filtrate the amount of antimony of Valentinite and antimonite. The content of individual mineral forms of antimony is determined by calculation 3. The disadvantage of this method is that when using its basic techniques, complete dissolution (or insolubility) of lead-iron sulfosalt antimony-jemocite (Pb FeSb) is not achieved, therefore the antimony of the latter cannot be isolated

3787374 4.

In a separate phase or on the edge - Table 1 presents the solubility

At least, it is determined in the amount of the gemonineral fraction of Jamsonite c.

antimony antimonite, which makes the conditions of the known methods of phase

method unsuitable for analysis of antimony ores and their products

Jamsonite ore processing.

Solvent and Dissolution Conditions

Boiling with 50 ml of 10% solution

Na, 2.S 2 h.77,9

Boil with 50 ml 2 n. solution.

NaOH 20 min67.2

Stirring with 50 ml 3 n. solution

HC1, containing 5% HjtOj, 30 min48.2

The aim of the invention is to determine within 18-20 hours the determination of the antimony of Jamsonite and the filtration of the antimony of Jamsonite, and in the axis into a separate phase with simultaneous antimony tetroxide. Determination of other mineral forms The second weighed amount of the initial material antimony .- at room temperature, the goal set is achieved by bathing 0.5-1.0 n. NaOH solution, which contains 5–10% vol. glycerin containing a portion of the starting material, is boiled over a period of 15–20 min at boiling with a solution of wine –– for 15–20 min, and the filtrate of the optic acid is obtained; the amount of antimony trioxide and anhydride are determined; and thymonite pentoxide, by subtracting from which the anthrax, and the residue, successively 30 antimony antimony holding, obtained by processing at 1 oat temp when analyzing the first sample, grade 0.5–1.0 n. NaOH solution, antimony trioxide content. holding 5–10 vol% glycerol, in the sequence of performing a 15–20 min report and in the filtrate of certain operations, the antimonite antimony is combined, and then 35 ba of the determination of antimony compounds in rub –9n. The solution of hydrochloric acid, soda and products of their processing with pre-containment of 5-10 vol.% of hydrogen peroxide is shown in the diagram.

First linkage

Boil with 50 ml of 10% tartaric acid for 30 min.

Filtrate Residue Sb trioxide and pentoxide -. A% Filtrate Sb antimonite - B% Filtrate Sb Jamsonite

Table 1

Antimony was found in the filtrate,% Stirring with 50 ml 0.51, 0 n. NaOH solution containing 5-10% oh. glycerol at 18-20C for 15-20 min. Residue Infusion with 50 ml of 6-9 n. HCl solution containing 510% w / v. , at 18–20 ° C. 18–20 h. Residue b, tetroxide, Second h.

Stirring with 50 ml 0.5-1.0 and. NaOH solution containing 5-10 vol.% glycerol at 18-20 C for 15-20 min

Filtrate

Sb trioxide and antimonite - In%

In the development of the method, chemically pure preparations and Sb2.0g are used, and such monomine fraction of senarmontite (), antimonite (SbuSo,) and Jamsonite are used. Chemically pure preparation Sbe.04 is obtained by calcination with TSO-HEO C. When choosing solvents and dissolution conditions, the concentrations of the solvent components, the processing time and the temperature mode vary. In all cases, weights of the surfactants are used.

Do not analyze

paraty and monomener fraction of 50-100 mg and the volume of solvent 50 ml. 5 Antimony in filtrates and residues is determined by titration with potassium bromate or photocolorimetrically based on the formation of an iodide-antimony complex.

In tab. 2 presents the results

20 characterizing the degree of dissolution of monomineral fractions and antimony preparations, depending on the solvent

L and processing conditions.

Table 2

Boiling with a 10% solution of 100.0 tromic acid rum for 30 min. Stirring with 0.5 n. NaOH solution for 15 minutes at 18-200 ° C 40.2: Mixing with a solution of NaOH containing 5% by volume of glycerin, 15 minutes at 1820 0 at an NaOH concentration of 0.5 n.99.8 1.0 n.99.8 2, 0 n.99.9 Stirring with 0.5 n. NaOH solution containing 10 vol.% glycerin, 15 min at 18–20 С99.8 Infusion with HC1 solution, containing 5% w / v. N.O., 18-20 h at 18-200С at a concentration of HC1 3 n.96.8 6 n.99.6 9 n.99.8 Infusion from 6 n. a solution of NS 1 soderztsim 1o% wt./about. H5 O5 18-20 hours at 18-20 ° С, ... 99.8) Solubility of the monoenergic fraction of the SbaO-j preparation,

2.3

3.4

1.1

100.0 Traces 3.2 92.4 1.5 0.4 6.5 6.5 98.7 3.2 0.7 8.3 99.2 5.5 0.6 13D 99.2 10.3 0.4 7.2 99.0 3.5 1.5 97.4 53.2 96.8 1.8 97.0 94.9 99.7 3.8 98.5 98.7 99.6 5.197.5 95.399, 6 enarmontita similar dissolveKak can be seen from the table. 2, when boiling with a 10% tartaric acid solution, antimony tri-pentooxide is completely dissolved, and the residue is stored with sulfide minerals and tetroxide. With stirring from 0.5N. 92.4% antimony of antimonite is dissolved with NaOH solution at room temperature, and this treatment practically does not affect Jamsonite antimony. In order to obtain satisfactory results of the phase analysis of antimony ores, it is necessary to increase the solubility of antimonite to almost complete, since antimitic is the dominant mineral form of antimony in ores. An increase in the solubility of antimonite with a comparatively small increase in the solubility of jamsonite (up to 3.2% in a 0.5N solution of NaOH) is achieved by introducing 5 vol.% Glycerol into the solvent. The increase in alkali content in the mixture to 2n. Concentrations are accompanied by an increase in the solubility of the jam sonite to 10.3% without noticeable effect on the solubility of the antimonite. If we neglect the increase in the solubility of jamsonite to 5.5% and Sb / jOg to 8.5%, then it is possible to use 1 n. NaOH solvent. From tab. 2 it can be seen that increasing the concentration of glycerol in the mixture to 10 vol.% Does not cause noticeable changes in the solubility of some forms of antimony, however, the use of too high concentrations of glycerin is undesirable due to the need for its oxidation during the subsequent determination of antimony in the stretch. The high degree of separation of anti-monitored anti-monite from jamsonite, as well as the almost complete solubility in the above mentioned solvent, antimony trioxide, allows to determine by the difference between the amount of cypbNttj, converted to alkaline-glycerol extract without pre-treatment with tartaric acid solution from the second sample, and antimony content in the analogous extract from the first sample, after the extraction of antimony of tri- and pentooxide by treatment with tartrate solution. When sampling the solvent and dissolution conditions for Jamsonite, the main criterion is the completeness of the dissolution of Jamsonite with the minimum solubility of antimony tetroxide, which is determined in the residue. When heated with hydrochloric acid solutions, a significant solubility of antimony tetroxide is observed, therefore the dissolution with a mixture of hydrochloric acid and hydrogen peroxide is carried out at room temperature. The almost complete dissolution of the monomineral fraction of jamsonite (over 95%) with relatively low solubility (1.53, 8%) is achieved at 3–9 n. Concentration of hydrochloric acid, containing 5% w / v, hydrogen peroxide. However, when processing a sample of jamsonite ore (C-3), tartaric acid and alkali-glycerin mixture 3 n were predissolved. about 27% of the total antimony is preserved in the residue with a solution of hydrochloric acid containing hydrogen peroxide, which indicates an incomplete dissolution of Jamsonite antimony under these conditions. The reason for the decrease in the solubility of antimony Jamsonite, apparently, is the enveloping of the mineral particles with silicate components of the hand, caused by the previous treatment with sodium hydroxide solution. With 6-9 n. The concentration of hydrochloric acid in the mixture used is the oxidation of Jamsonite proceeds more intensively, accompanied by an increase in the solubility of the determined fraction in the ore. In these cases, the antimony residue in the C-3 ore after treatment with a mixture of hydrochloric acid and hydrogen peroxide does not exceed 3-4.5% of the total. Thus, for the phase determination of Jamsonite in the corresponding ore should be used a concentration of hydrochloric acid not lower than bn. Increasing the concentration of hydrogen peroxide in the mixture to 10% w / v. The solubility increases to D 5 5.1%; however, this increase does not introduce significant changes in the results of the analysis due to the very low content of antimony tetroxide in antimony ores. In order to eliminate the influence of chloride ions, when determining antimony in the form of an iodine-antimony complex in hydrochloric filtrates, a calibration graph was used that was constructed at a constant concentration of hydrochloric acid. Since it is difficult to maintain a constant concentration of hydrochloric acid during the phase determination of antimony jamsonite due to the oxidation of a part of chloride ions with hydrogen peroxide to free chlorine, the concentration of hydrochloric acid in the analyzed solution is determined by titrating an aliquot part of a 1N solution. sodium hydroxide solution for phenolphthalein. When an iodine-complex is formed, the concentration of hydrochloric acid is adjusted to a constant value by adding a calculated volume of 6 n. solution of NS t. Hydrogen peroxide present in a hydrochloric acid solution almost completely decomposes under prolonged infusion conditions and does not cause oxidation of iodide ions in the determination of antimony. In cases where the oxidation of iodide does occur, it can be prevented by adding a few drops of a 2% thiourea solution. Example. Determination of total antimony content. A weighed sample of 0.100, 50 g of ore is placed in a 100 ml conical flask, 10 ml of concentrated nitric acid and 25 ml of concentrated sulfuric acid are poured, and evaporated to a thick vapor of sulfuric anhydride. Close the flask with a funnel and heat it strongly until the solution lightens and the insoluble residue is completely whitened. To the cooled solution, 5-10 ml of water are added, washing the walls of the flask, and the evaporation is repeated. After cooling, 30-40 ml of water are poured, boiled until the salts are completely dissolved, cooled again and transfer the solution to a 100 ml volumetric flask, water is added to the mark with distilled water and stirred. From the supernatant solution, an aliquot of 20 ml or less is carefully taken, depending on the content of the bottle, into a 50 ml volumetric flask. When taking an aliquot of less than 20 MP, a solution of sulfuric acid (1: 3) is added to a volume of 20 ml. 10 ml of 15% w / v solution of potassium iodide containing 1% thiourea are added to aliquot and added to the mark with water. After adding each reagent, the solution is stirred. Optical density is measured using a photocoremeter in cuvettes with a layer thickness 20 mm with a light filter having a maximum transmission of 400 nm using a comparison solution containing 20 ml of sulfuric acid (1: 3) and 10 ml of iodide solution {ali with thiourea. The content of antimony is determined using a calibration chart 50 ml flasks are sampled 0,1,2 , 3,4,6,8 and 10 ml of a standard solution containing 0.1 mg of surfactant in 1 ml of a sulphate solution (1: 3 is added to a volume of 20 ml of a solution of hydrochloric acid (1: 3), 10 ml of The potassium with thiourea is adjusted to the mark with water and the optical density is measured in cuvettes with a layer thickness of 20 mm. Example 2. Determination of the sum of antimony trioxide and pentooxide. The ore sample is 0.5 g or less, depending on from the expected content, placed in a 100 ml beaker, poured into a 10% tartaric acid solution, stirred, heated to boiling and boiled for 30 minutes, from time to time e volume before the initial hot water. The solution is filtered and the filter is cut into a 100 ml volumetric flask. The residue is washed with small portions of a hot 2% solution of tartaric acid, and the volume is added to the mark with the same solution. The solution is stirred, a 20 ml liquid portion is withdrawn into a 50 ml volumetric flask, 10 ml of sulfuric acid solution (1: 1) is added, cooled, 10 ml of potassium dihydrogen and thiourea are added and brought to the mark with water. After adding each reagent, the solution is thoroughly mixed. The solution is photocolorimetric and the amount of antimony trioxide and pentooxide is determined in percent relative to the weight (A%). Example 3. Determination of antimonite antimony. The residue after treatment with tartaric acid is washed from the filter into the same glass with distilled water, 5 ml of 5N are added. a solution of caustic soda and 5 ml of a solution of glycerin (1: 1), the volume is adjusted to 50 ml with water and stirred for 15 minutes manually or using a magnetic stirrer. The solution is filtered through a dense filter into a 100 ml volumetric flask. Ongstock in the glass and on the filter is washed several times with 0.5 n. sodium hydroxide solution containing 5% vol. glycerol. The volume is made up to the mark with the same solution and mixed. An aliquot of 20 ml or less, depending on the expected content, is placed in a 100 ml conical flask, 5 ml of concentrated sulfuric acid is added and evaporated on a hotplate. When the solution darkens, carefully add 2-3 ml of 30% hydrogen peroxide solution and continue heating. The addition of hydrogen peroxide is repeated until the solution remains colorless after the perhydrol is decomposed. 15-20 ml of water are added to the sulphate solution, cooled, transferred to a 50 ml volumetric flask and antimonite antimony (B%) is determined by photocolorimetric, as described in Example 1. Example 4. Determination of Jamsonite antimony. After obtaining the alkaline extract, the filter residue was washed into the same glass with 10-15 ml of water, 8 ml of 30% hydrogen peroxide, 25 ml of concentrated hydrochloric acid were added, the volume was adjusted to 50 ml with water, and the glass was placed in the cupboard and leave until next day. During the working time, the contents of the glass are mixed several times with a glass rod. After 18–20 hours, the hydrochloric acid solution is filtered through a thick filter paper into a 100 ml volumetric flask, washing the precipitate on the filter several times with hot 3N. hydrochloric acid solution. The volume is adjusted to the mark with the same solution and mixed. The concentration of hydrochloric acid in photocolorized solutions is adjusted to a constant value (0.9 N.) by the addition of 6N. hydrochloric acid solution. To determine the concentration of hydrochloric acid, 2 ml of the test solution is placed in a 100 ml conical flask, diluted with distilled water to 15–20 ml and titrated with 1N titrated sodium hydroxide solution

or potassium according to phenolphthalein. The amount of titrated solution of 6 n hydrochloric acid (X) in MP, added for. ydderzhaniya constant kontrashschii chloride of ions calculated by the formula

y - 4S-TV

 - t,

where T is found titrimetrically

the concentration of hydrochloric acid in the extract, mol / l, V is the volume of the acid acid extract taken to determine the antimony MJ, MP.

To determine antimony in a saline solution, a 50 ml aliquot is placed in a 50 ml measuring bottle with an aliquot of 10 ml or less of the mixed solution and a volume of titrated 6 n is added. hydrochloric acid solution found by Equation. Antimony is determined as described in Example 1 using a calibration graph constructed with the addition of hydrochloric acid to 0.9 N concentration

0.20 0.05 U, 01

CA-1 1.62

0.16 0.14 0.01

1.62

CA-1

1.55 0.16 0.16 0.03 1.28

X-6

1.55 0.14 0.13 0.03 1.28

 X-6

As can be seen from the table. 3, the proposed method makes it possible to efficiently determine and isolate the antimony of jamsonite in a separate phase while simultaneously determining other mineral forms of antimony in antimony ores and their enrichment products.

Claims (3)

1. A method for determining antimony compounds in ores and their re-example 5. The determination of antimony tetroxide. The residue from the hydrochloric acid extract together with the filter is placed in a 100 ml conical flask and antimony is determined as described in Example 1.  Example 6. Determination of antimonite and trioxide antimony cyMhM. A separate sample of 0.1-0.5 g is placed in a 100 ml beaker and treated as described in Example 3. From the amount of antimony found in this case (B%), the antimonite antimony content (B%) is subtracted and the percentage of antimony is found trioxide in the analyzed material 5Sbsb in - B The content of antimony pentoxide is calculated from the difference between the total amount of oxide antimony (A%) and the found content of antimony trioxide 0Sbsb-t. A - (B - B) In tab. 3 shows the results of the phase analysis of samples of antimonite and jamsonite ore according to the proposed scheme. T a b l and c a 3 1.57 1.32 Not found 1.71 1.40 Not found 1.63 1.58 processing, including sequential and selective treatment of the starting material weights with various solvents, while one sample is treated at the boil with a solution of tartaric acid to produce a filtrate containing a sum of antimony three-and pentoxide and the residue, followed by analysis of the antimony forms from known methods, About tl and h ay u and with the fact that, for the purpose of you, dividing the antimony of jamsonite into a separate phase, the residue is sequentially processed from 0.5 to 1.0 n. NaOH solution containing 5-10 vol.% glycerol for 15-20 min and antimonite antimony in the filtrate, and then 6-9 n. with a solution of hydrochloric acid containing 5-10 vol.% of hydrogen peroxide for 18–20 hours and in the filtrate, jamsonite antimony is determined. 2. The method according to Claim 1, exc and ayuts and in order to determine the antimony trioxide, the second sample of the starting material is 0.5-1.0 n. NaOH solution containing 5-10 vol.% glycerol for 15-20 minutes and in the filtrate the amount of antimony trioxide and antimonite is determined. Sources of information taken into account during the examination 1. Dolivo-Dobrovolsky V.V. and others. Rational Angshiz ores. M., Metallurgizdat, 1947, p. 140. 2. Factory Laboratory, 1973, vol. 39, 5, p. 539. 3.Solntsev N.I. and others. Sat. scientific works Gintsvetmeta. M., Metgshlurgizdat, 1956, 12, p. 24